Technique for emulsifying highly saturated hydroisomerized fluids

ABSTRACT

A preferred emulsifier blend includes ethoxylated alcohols containing hydrocarbons of C10-C16 and preferably having on average at least 2.8 ethoxy and/or alcohol groups per chain and a glycerol mono- and/or dioleates, preferably in a ratio of from 9:1 to 4:6. These emulsion blends are particularly useful when mixed with hydroisomerized oils and water, for subsequent application as a spray oil to agricultural crops. The emulsion blends of the present invention also find particular utility when mixed with conventional spray oils and hard water.

RELATED APPLICATION

The present application is a divisional application of U.S. patentapplication Ser. No. 09/783,497, filed Feb. 13, 2001, now U.S. Pat. No.6,515,031, which is incorporated by reference herein in its entirety.

FIELD OF THE INVENTION

The present invention relates emulsifiers for highly saturated,hydrocracked and/or hydroisomerized fluids. More particularly, thepresent invention relates to compositions containing emulsified, highlysaturated hydrocracked, and/or hydroisomerized oils particular usefulwhen applied to crops.

BACKGROUND OF THE INVENTION

Petroleum oils have long been sprayed on agricultural crops as a meansof pest control. Properly processed petroleum oils are generally lessphytotoxic than many synthetic pesticides, with the resulting oil coveraffecting the target mites, flies, bugs, scales, aphids and the like buthaving little deleterious effect on the target tree, plant or crop.

Conventional spray oils are manufactured from crude oil and petroleumfractions using conventional solvent refining techniques or usinghydro-treated base oils. Typically, the higher the paraffinic content(i.e., the proportion of saturated straight or branched hydrocarbonchains) in the oil, the more effective the oil is against pests and theless phytotoxic it is to plants. Oils containing high normal paraffiniccontents can lead to an elevated pour temperature, which can causeproblems when the oil is applied as a spray oil in colder climates.

Finished spray oils typically include 1 to 3 weight percent (wt %) of anemulsifier to allow the oil to remain emulsified in a water carrierduring spraying. Conventional emulsifiers for this purpose include alkylphenol ethoxylates.

Although such alkyl phenol ethoxylates perform satisfactorily under mostconditions, their emulsification capability decreases substantiallyunder hard water conditions. When conventional spray oils emulsifiedwith alkyl phenol ethoxylates and hard water, separation can occurduring or shortly after spraying, in which case the non-emulsified oilor other composition constituents separate out on the plant leaf,causing phytotoxicity which may be evidenced by leaf browning.

Severely hydrocracked and/or severely hydrocracked hydroisomerized oils,having a saturate content of ≧99% and/or exhibiting a high degree ofbranching of the paraffin molecules, are now available. Exemplaryseverely hydrocracked and hydroisomerized oils include the Spray Oil 10,Spray Oil 13, Spray Oil 15 and Spray Oil 22 hydrocracked andhyroisomerized oils available from Petro-Canada Lubricants ofMississauga, Ontario L5K 1A8, Canada, characteristics of which aresummarized below:

Spray Spray Spray Oil Oil Spray Oil Oil Quality Test Method 1 13 15 22Appearance Visual clear clear clear clear bright bright bright brightColor ASTM D1500 <0.5 <0.5 <0.5 <0.5 Density @ ASTM D1298 0.83 0.84 0.840.84 15° C. kg/l kg/l kg/l kg/l Viscosity @ ASTM D445  9.5 cSt 20.0 cSt20.0 cSt 20.0 cSt 40° C. Analine ASTM D611  103 113 113 113 PointNitrogen ASTM D4629 <1 ppm <1 ppm <1 ppm <1 ppm Sulphur ASTM D5453 <1ppm <1 ppm <1 ppm <1 ppm Saturates PCM 528 >99.9 >99.9 >99.9 >99.9 wt %wt % wt % wt % Aromatics PCM 528 <0.1 wt % 0.1 0.1 wt % 0.1 wt % wt %Polynuclear HRMS <1 ppm <1 ppm <1 ppm <1 ppm aromatics

The hydrotreating or hydrocracking step can be carried out in thepresence of a catalyst based group VIB and VIII metals, oralternatively, in the presence of a catalyst based on a crystallinesilicoaluminophosphate molecular sieve. Typical hydrocracking orhydrotreating conditions include temperatures of from 200 to 450° C.,hydrogen pressures of from 400 to 5,000 psig, a hydrogen circulationrate of 400 to 15,000 SCF/B and space velocities of from 0.1 to 20 hr-1.Hydroisomerization is typically carried out after the hydrocracking orhydrotreating step using a crystalline silico-aluminophosphate molecularsieve catalyst, which optionally contains group VIII and IIA metals. Theprocess is carried out at a temperature of from 250 to 450° C., athydrogen pressures of from 100 to 5000 psig, a hydrogen circulation rateof 400 to 15,000 SCF/B and liquid hourly space velocity of 0.1 to 20hr-1. The hydroisomerized fluid is hydrofinished at temperatures of from190 to 340° C. and pressures of from 400 to 500 psig, a hydrogencirculation rate of 400 to 15,000 SCF/B, in the presence of a solidmetal hydrogenation catalyst. The initial hydrotreating or hydrocrackingstep can be carried out in the presence of a catalyst based group VIBand VIII metals, or alternatively, in the presence of a catalyst basedon a crystalline silicoaluminophosphate molecular sieve. Typicalhydrocracking or hydrotreating conditions include temperatures of from200 to 450° C., hydrogen pressures of from 400 to 5,000 psig, a hydrogencirculation rate of 400 to 15,000 SCF/B and space velocities of from 0.1to 20 hr-1. Typically, the finished product has a natural pour point offrom −30 to −60° C., and below, with a preferred pour point of below−50° C.

While the above techniques are used to produce severely hydrocracked andhydroisomerized fluids, issues of adequate emulsification performanceunder hard water conditions present with such fluids can also be presentwith fluids which are not hydroisomerized but are hydrocracked orobtained through solvent extraction and contain 80-95 wt % or moresaturates. As used herein the phrase hydrocracked and/or hydroisomerizedfluids includes organic fluids which are either hydrocracked orhydroisomerized or both and contain a saturate content of >80%. Examplesof such fluids available from suppliers other than Petro-Canada aredescribed below:

Chevron SunSpray Quality Test Method Exxon 100N 100R 11N AppearanceVisual clear/bright clear/ clear/ bright bright Color ASTM <0.5 <0.5<0.5 D1500 Density @ ASTM 0.8639 0.8551 0.857 15° C. D1298 Viscosity @ASTM 20.24 20.52 19.28 40° C. D445  Analine Point ASTM 97.6 106.4 101.9D611  Saturates PCM 528 81.2 95.6 93.0 Aromatics PCM 528 18.8 4.4 7.0Polynuclear HRMS 5.8 1.2 1.7 aromatics

Unfortunately, hydrocracked and/or hydroisomerized fluids are notreadily usable as spray oils because they are often less soluble thenconventional oils. As a result of this poorer solubility, the otherwiseconventional alkyl phenol emulsifiers tend to drop out of solution uponstanding. Conventionally used emulsifiers do not seem to performadequately and do not have the required storage stability when added tohydrocracking and/or hydroisomerized oils.

The emulsification capability of a potential emulsifier may be evaluatedby considering its hydrophile/lipophile balance (hereinafter HLB value).The HLB value, which is an approximate measure of polarity, usuallyranges from 2-18. The higher the number, the more polar the subjectmolecule—the lower the number, the less polar the subject molecule. Themore polar molecules are generally more soluble in water and the lesspolar molecules generally more soluble in oil. However, in evaluatingpotential emulsifiers for use with hydroisomerized fluids, the HLBvalues have proven to have poor predictive value, with no singleemulsifier performing satisfactorily.

Below is a list of commercially available emulsifiers, which were testedfor emulsification ability with hydrocracking and hydroisomerizedfluids, including emulsifier class, source, product name, HLB value,average number of ethoxylate or alcohol groups per molecule, and carbonchain numbers, if known.

emulsifier # EO/ class source product name HLB OH C Chain ethoxylatedDe- Delonic LF-EP-18 6.0 alcohol forest¹ Delonic LF-EP-20 6.2 DelonicLF-EP-25 7.0 Delonic LF-EP-30 8.0 ethoxylated Shell² Neodol 23-3 7.9  2.9 C12-C13 alcohol Neodol-23-1 3.7 1 C12-C13 Neodol 25-3 7.5   2.8C12-C13; C14-C15 Neodol 1-3 8.7 3 C11 sorbitan ICI³ SPAN 80 4.3monooleate ethoxylated Synperonic A4 9.1 4 C13-C15 alcohol Synperonic A37.9 3 C13-C15 polyoxy- Brij 30 9.7 4 C16-C18 ethylene Brij 93 4.9 2lauryl ether

emulsifier # EO/ class source product name HLB OH C Chain ethoxylatedDe- Delonic LF-EP-18 6.0 alcohol forest¹ Delonic LF-EP-20 6.2 DelonicLF-EP-25 7.0 Delonic LF-EP-30 8.0 ethoxylated Shell² Neodol 23-3 7.9 2.9C12-C13 alcohol Neodol-23-1 7.9 2.9 C12-C13 Neodol 25-3 3.7 3.7 C12-C13;C14-C15 Neodol 1-3 8.7 8.7 C11 sorbitan ICI³ SPAN 80 4.3 monooleateethoxylated Synperonic A4 9.1 4 C13-C15 alcohol Synperonic A3 7.9 3C13-C15 poly- Brij 30 9.7 4 oxyethylene Brij 93 4.9 2 lauryl ether

None of these emulsifiers alone provided satisfactory emulsificationwith Spray Oil 22 and Spray Oil 10 hydrocracked and hydroisomerizedfluids.

It can be see there remains a continuing need for an emulsifier that canemulsify hydrocracked and/or hydroisomerized fluids. There remains afurther need for such an emulsifier for use with hydrocracked and/orhydroisomerized fluids, which will result in an emulsified product whichis satisfactory for use in agricultural applications as a spray oil. Inaddition, there remains a need for an emulsifier adaptable for use withconventional spray oils as well as hydroisomerized spray oils, that willmaintain emulsification ability when solubilized in hard water, so as tominimize phytotoxicity to the plants to which such spray oils areapplied. It is against this background that the techniques of thepresent invention have been developed.

SUMMARY OF THE INVENTION

The emulsifier blends of the present invention include ethoxylatedalcohols containing C10-C16 carbon chains having on average 2.8 or moreethoxy or alcohol groups per carbon chain together with glycerol mono-,di- and/or trioleates. A preferred emulsifier blend of the presentinvention contains ethoxylated alcohol:glycol mono- and/or dioleates ina ratio of wt % of from 9:1 to 4:6. Said another way, a preferredemulsifier blend of the present invention contains from 90% to 40% byweight of ethoxylated alcohols and 10% to 60% of a mixture of glycolmono and/or dioleates. A more preferred emulsifier blend containsC12-C16 carbon chains and contains ethoxylated alcohols and glycerolmono- and/or dioleates in a ratio of 9:1 to about 6:4. A most preferredratio of ethoxylated alcohols and glycerol mono- and/or dioleates is4:1.

The emulsifier blends of the present invention find particular utilityin the emulsification of hydrocracked and/or hydroisomerized fluids,especially oils, which may then be employed as spray oils for subsequentapplication to agricultural crops. The emulsifier blends of the presentinvention are also very useful in emulsifying conventional spray oils inhard water, prior to application to agricultural crops.

DETAILED DESCRIPTION

The emulsifier blends of the present invention include ethoxylatedalcohols containing C10-C16 carbon chains having on average at 2.8 ormore ethoxy or alcohol groups per carbon chain together with glycerolmono- and/or dioleates. A preferred emulsifier blend of the presentinvention contains ethoxylated alcohol:glycol mono- and/or dioleates ina ratio of wt % of from 9:1 to 4:6. Said another way, a preferredemulsifier blend of the present invention contains from 90% to 40% byweight of ethoxylated alcohols and 10% to 60% of a mixture of glycolmono and/or dioleates. A more preferred emulsifier blend containsC12-C16 carbon chains and contains ethoxylated alcohols and glycerolmono- and/or dioleates in a ratio of 9:1 to about 6:4. A most preferredratio of ethoxylated alcohols and glycerol mono- and/or dioleates is4:1.

The process of evaluating and identifying a preferred ethoxylatedalcohol/glycerol dioleate composition is further described below inExample I.

EXAMPLE I

As summarized in Table I below, 0.5 grams of each ethoxylated alcoholproduct was weighed and added, with mixing, at room temperature, to abeaker containing 50 grams of the Spray Oil 10 hydrocracked andhydroisomerized oil. Added to the oil was 0.3 grams of a rapeseed mono-and diglyceride product obtained from Rhodia Canada, Inc. under thetradename Alkamuls GMR-55-LG, with mixing. When difficulty insolubilizing occurred or turbidity occurred, the preparation was warmedslightly. The oil/emulsifier blend was set aside for 12-24 hours toconfirm no additional separation had occurred. To quantify emulsifierperformance, 1 ml of the oil/emulsifier blend was added to a 100 mlgraduated cylinder of water. The graduated cylinder was then pluggedwith a stopper, inverted 10 times to allow proper distribution of theoil. The stopper was then removed and a timer started. The timer wasstopped when 1 ml of fluid had separated to form a top oil layer.Product performance was characterized as poor (1 ml top layer in <45seconds), good (1 ml layer in ≧45 seconds but <90 seconds), andexcellent (1 ml layer in ≧90 seconds). Performance is summarized inTable I.

TABLE I ethoxylated hydro- Time to alcohol # carbon 1 ml per- productamount HLB EO chain separation formance Synperonic A2 0.5 gm 5.9 2C13-C15 10 sec poor Synperonic A3 0.5 gm 7.9 3 C13-C15 45 sec goodSynperonic A4 0.5 gm 9.1 4 C13-C15 95 sec excellent Rhodasurf L-4 0.5 gm9.7 4 C10-C16 251 sec  excellent Brij 93 0.5 gm 4.9 2 15 sec poor Renex30 0.5 gm 14.5 12 C30 ether 27 sec poor

It can be seen that an emulsifier blends of the present inventioncontaining an ethoxylated alcohol comprising primarily C10-C16hydrocarbon chains with an average of 3 or more ethoxylate or alcoholgroups, in combination with glycerol mono- and/or dioleates,satisfactorily emulsifies the Spray Oil 10 product tested.

EXAMPLE II

To a beaker containing 50 grams of Spray Oil 10 hydrocracked andhydroisomerized oil was added 1.0 grams of Rhodasurf L-4 ethoxylatedalcohol along with a listed amount of Alkamuls GMR-55-LGmono/diglyercide product. 1 ml of each such oil/emulsifier blend wasthen added to a 100 ml graduated cylinder of water which was pluggedwith a stopper and inverted 10 times. The stopper was removed and atimer started. The timer was stopped when 1 ml of fluid had separated toform a top layer. Product performance was characterized as above andsummarized in Table II.

TABLE II ethoxylated No. hydro-C glycol Time to alcohol amount HLB EOchain dioleate 1 ml separ. performance Rhodasurf L-4   1 gm 9.1 4C10-C16 0.0 gm 22 poor Rhodasurf L-4 0.9 gm 9.1 4 C10-C16 0.1 gm 63 goodRhodasurf L-4 0.8 gm 9.1 4 C10-C16 0.2 gm 148  excellent Rhodasurf L-40.7 gm 9.1 4 C10-C16 0.3 gm 55 good Rhodasurf L-4 0.6 gm 9.1 4 C10-C160.4 gm 85 good Rhodasurf L-4 0.5 gm 9.1 4 C10-C16 0.5 gm 48 goodRhodasurf L-4 0.4 gm 9.1 4 C10-C16 0.6 gm 51 good Rhodasurf L-4 0.3 gm9.1 4 C10-C16 0.7 gm 13 poor Rhodasurf L-4 0.2 gm 9.1 4 C10-C16 0.8 gml18 poor Rhodasurf L-4 none 9.1 4 C10-C16 1.0 ml 11 poor

Based on these results, a preferred emulsifier blend of the presentinvention contains ethoxylated alcohol:glycol mono- and/or dioleate in aratio of wt % from 9:1 to 4:6. Said another way, a preferred emulsifierblend of the present invention contains from 90% to 40% by weight ofethoxylated alcohols and 10% to 60% of a mixture of glycol mono and/ordioleates. A more preferred emulsifier blend contains C12-C16 carbonchains. A more preferred emulsifier blend also contains ethoxylatedalcohols and glycerol mono- and/or dioleates in a ratio of 9:1 to about6:4. A most preferred ratio of ethoxylated alcohols and glycerol mono-and/or dioleates is 4:1.

EXAMPLE III

To a beaker containing 100 grams of Spray Oil 22™ hydrocracked andhydroisomerized oil was added 1.4 grams of one of the various Neodolethoxylated alcohol products available from Shell Oil Co., plus 0.06 gmAlkamuls GMR-55-LG mono/diglyercide product. 1 ml of each suchoil/emulsifier blend was then added to a 100 ml graduated cylinder ofwater which was plugged with a stopper and inverted 10 times. Thestopper was removed and a timer started. The timer was stopped when 1 mlof fluid had separated to form a top layer. Product performance wascharacterized as above and summarized in Table III.

TABLE III ethoxylated hydro-C Time to 1 ml alcohol HLB # EO chainseparation performance Neodol 91-6 12.4 6 C9/C10, C11 6 poor Neodol91-2.5 8.5 2.7 C9/C10, C11 20 poor Neodol 1-5 11.2 5 C11 22 poor Neodol23-1 3.7 1 C12/C13 23 poor Neodol 25-3 7.5 2.8 C12/C13 90 excellentC14/C15 Neodol 1-3 8.7 3 C11 98 excellent Neodol 23-6.5 12.0 6.6 C12/C13131 excellent

The above example demonstrates that the preferred ethoxylated alcoholscontain predominantly hydrocarbon chains of length C11 or more, mostpreferably C12/C13 hydrocarbon chains, and contain on average at least2.8 ethoxylate groups per chain.

EXAMPLE IV

To test the emulsifier blend of the present invention with the Exxon100N, Chevron 100R and SunSpray 11N hydrocracked and/or hydroisomerizedoils described above, a beaker containing 100 grams of each oil wasmixed with either 1.6 grams of TMulzA02 (“known emulsifier”) or 1.12grams of Rhodasurf L-4 plus 0.48 grams Alkamuls GMR-55-LGmono/diglyercide product (“new emulsifier”). 1 ml of each suchoil/emulsifier blend was then added to a 100 ml graduated cylinder ofwater which was plugged with a stopper and inverted 10 times. Thestopper was removed and a timer started. The timer was stopped when 1 mlof fluid had separated to form a top layer. Product performance wascharacterized as above and summarized in Table IV.

TABLE IV Time to 1 ml Base oil separation performance Exxon 100N newemulsifier 173 excellent Exxon 100N known emulsifier 390 excellentChevron 100R new emulsifier 85 good Chevron 100R known emulsifier 53good SunSpray 11N new emulsifier 535 excellent SunSpray 11N knownemulsifier 35 poor

It can be seen that use of an emulsifier blend of the present inventionwith each of the above-listed base oils resulted in product performancewhich was either good or excellent. In addition, it can be seen thatbase oil performance improved for both the Chevron 100R and SunSpray 11Nproducts when used with an emulsifier blend of the present invention.

EXAMPLE V

In what resulted in further unexpected results, an emulsion blend of thepresent invention was able to emulsify a standard spray oil in hardwater substantially better than a conventional emulsifier added to thespray oil. More particularly, an emulsion blend of the present inventioncontaining 70 wt % of Rhodasurf L4 was mixed with 30 wt % of theAlkamuls® GMR-55/LG glycerol mono and dioleate product described abovealong with 50 grams standard Spray Oil 10, a severely hydrocracked andhydroisomerized neutral base oil with additives, available fromPetro-Canada of Calgary, Alberta, Canada. One ml of this oil/emulsionblend was then added to 100 ml. of water obtained from 17 differentsites in California. Water from each these locations can becharacterized as hard water, as is apparent from the measured mineralcontent of a water sample from each of these sites, summarized in TableV(a) below.

TABLE V(a) Site Mineral Content of Water in ppm No. B Ca Si Mg Zn 1. 1.710.1 7.3 0.7 — 2. 1.4 31.5 8.9 4.8 — 3. 1.4 26.7 8.4 0.2 — 4. 1.1 7.45.2 0.2 — 5. 1.2 27.2 7.0 3.0 — 6. 1.1 51.5 6.9 5.3 — 7. 1.3 38.8 9.23.6 — 8. 1.0 30.5 5.5 2.7 — 9. 1.4 15.7 4.1 9.1 — 10. 1.0 2.9 1.7 0.4 —11. 1.4 52.7 11.6 2.9 — 12. 1.1 32.0 10.8 29.4 — 13. 1.2 36.9 9.6 8.0 —14. 0.5 116 4.3 38.6 1.1 15. 1.9 4.8 5.3 0.5 0.5 16. 1.8 4.6 5.0 0.5 —17. 2.0 4.9 5.7 0.5 0.5

Emulsification performance was timed as described as above in Examples Iand II, with the time required for a 1 ml top layer to separate listedbelow in Table V(b). Emulsion performance was then compared in each casewith emulsion performance of the Spray Oil 10 when combined with thelisted wt % of TMulz A02 FS02, a conventional emulsifier available formHarcros Chemicals, Inc. The separation times for these products, inminutes, to emulsion separation for each sample are also listed TableV(b).

TABLE V(b) Emulsifier Blend Emulsifier TMulz A02 FS02 1.0 1.2 1.4 1.61.0 1.2 1.4 1.6 1.8 Site wt % wt % wt % wt % wt % wt % wt % wt % wt %No. Emusifier performance in minutes to form separated 1 mllayer 1. >7 >7 >8 >8 <2 <2 <1 <2 <2 2. >8 >9 >10 >8 <1 <1 <1 <1 <3. >5 >6 >5 >7 <1 <1 <1 <1 <1 4. >10 >6 >4 >2 <1 <1 <1 <1 <15. >10 >7 >11 >15 <1 <1 <1 <1 <1 6. >8 >8 >12 >15 <1 <1 <1 <1 <17. >3 >4 >14 >23 <1 <1 <1 <1 <1 8. >6 >7 >11 >14 <1 <1 <1 <1 <19. >8 >8 >10 >13 <1 <1 <1 <1 <1 10. >9 >11 >16 >18 <1 <1 <1 <1 <211. >3 >3 >4 =7 <1 <1 <1 <1 <1 12. >4 >9 >12 >8 <1 <1 <1 <1 <113. >29 >36 >41 >48 <1 <1 <1 <1 <1 14. >2 >5 >5 >7 <1 <1 <1 <2 <215. >21 >27 >40 >62 <2 <2 <2 <2 <2 16. >6 >9 >16 >22 <1 <1 <1 <1 <117. >3 >3 >6 >12 <1 <1 <1 <1 <1

As is readily apparent from a review of the data, the emulsifier blendof the present invention maintained oil emulsification in all casesexcept one, for over 3 minutes, and many substantially over 3 minutes.In contrast, all of the tests using a convention emulsifier separated inless than 2 minutes, with over 85% of the samples separating in lessthan 1 minute.

Spray Oil Functionality

Phytotoxicity generally relates to injury to plants arising fromapplication of exogenous substances to plants. Such substances caninclude fertilizers, herbicides and other types of compounds applied toplant soil or to plant surfaces, such as by foliar spraying. Manysubstances have a safe application rates, at which phytotoxicity isnon-existent or de minimus, but can injure or kill plants at higherapplication rates. Other compounds are per se phytotoxic. As a generalrule, when applied as a physical barrier to treat pest infestation,lighter spray oils have less potential for phytotoxicity then equivalentbut heavier spray oils, but are often less effective for pest controlthan equivalent heavier spray oils. In order to increase pest controleffectiveness of the lighter spray oils, greater application rates aresometimes employed, but this approach too can result in increasedphytoxicity. As further discussed below, a decrease in phytoxicity hasbeen achieved by use of the emulsifier of the present invention, whenused with higher application rates of both lighter and heavier highlyhydroisomerized spray oils.

EXAMPLE VI

Spray oils were evaluated for phytotoxicity and for certaindisease-control factors in a grove of 11-year-old Ruby Red grapefruit(Citrus paradisi) on Swingle citrumelo (Poncirus trifoliata x C.sinensis) rootstock near Lake Alfred, Fla. Each treatment was applied tofive two-tree plots arranged in completely randomized design. Ten shootsper tree from the spring flush of growth were tagged in April 1999. Allproducts were applied to foliage from June 29 to Jul. 1, 1999 using ahandgun sprayer at 200 psi. The rate per acre indicated in the table wasadded to 125 gallons and the trees were sprayed using about threegallons per tree. An application of ethion was made on Jul. 9, 1999 tocontrol rust mite.

TABLE VI Applic. Treatment Description rate/acre Phytotox rating ControlNone 0.00 Spray Oil 15 + new emulsifier 10 gal 1.12 Spray Oil 15 + knownemulsifier 10 gal 1.08 Spray Oil 22 + new emulsifier 10 gal 1.03 SprayOil 22 + known emulsifier 10 gal 1.12 Spray Oil 15 + new emulsifier 15gal 1.06 Spray Oil 15 + known emulsifier 15 gal 1.43 Spray Oil 22 + newemulsifier 15 gal 1.00 Spray Oil 22 + known emulsifier 15 gal 1.40Sunspray oil (455) + known emulsifier 10 gal 0.97 Sunspray oil (455) +known emulsifier 15 gal 1.34

Phytotoxicity symptoms were noted on leaves on the spring flush ofgrowth. Most oil sprays produced a raised blister type of symptom whichhad a superficial resemblance to greasy spot, but no chlorosis wasassociated with these symptoms. Of the Petro-Canada oils, there was nodifference between the phytotoxicity rating for Spray Oil 15, rated at1.17 and Spray Oil 22, rated at 1.14. The average rating for Sunspray455 was 1.16.

However, the average for the treatments with the conventional emulsifierwas significantly higher than the treatments with the new emulsifier(1.26 as compared to 1.05) and this was especially evident at the15-gallon rate. No defoliation was associated with the leaf damagecaused by the oils.

Bearing in mind that the Petro-Canada oil and Sunspray oil treatmentsmay be preferred for pest control over traditional “chemical”insecticide treatments like the BASF 500-00F 2.07 EC, traditional metaltreatments like the copper-based Kocide 2000 product, and traditionalfungicides like Flint 50, with the heavier weight oils and heavierapplication preferred, the reduction in phytotoxicity at a 15 gallonapplication rate for Spray Oil 22 and Spray Oil 15 by substitution ofthe known emulsifier with the new emulsifier of the present invention issignificant. More particularly, the reduction in phytotoxicity with agallon per acre application of Spray Oil 15 from 1.43 to 1.06 whenutilizing the emulsion of the present invention and the similarreduction in phytotoxicity with a 15 gallon per acre application SprayOil 22 from 1.40 to 1.00 is significant.

With respect to the disease control factors, all of the fungicidestested significantly reduced the severity of greasy spot on the springflush. The petroleum spray oil treatments controlled greasy spot, butresponse differed with the various oils. The average severity rating forthe 10-gallon rates for all oils, 0.05, and the average rating for the15-gallon rate, 0.14, were not significantly different. Most of the oiltreatments were as effective as the standard copper treatment.

EXAMPLE VII

Spray oils were evaluated for defoliation and marketable fruityields—both an aspect of phytotoxicity—and for certain disease-controlfactors, in the grove of 10-year-old Ruby Red grapefruit describedabove. Each treatment was applied to five two-tree plots arranged inrandomized complete block design. Ten shoots per tree from the springflush of growth were tagged in April 1998. All products were applied tofoliage from Jul. 7 to 9, 1998 using a handgun sprayer at 200 psi. Therate per acre indicated below was added to 125 gallons and the treeswere sprayed using about 3 gallons per tree.

TABLE VII % Application Defolia- % Marketable Treatment Descriptionrate/acre tion Fruit Control None 10.1 67.3 Spray Oil 13 w/newemulsifier 10 gal 4.4 73.3 Spray Oil 13 w/new emulsifier 20 gal 5.4 48.0Spray Oil 15 + new emulsifier 10 gal 4.4 73.3 Spray Oil 15 + knownemulsifier 10 gal 7.9 58.0 Spray Oil 15 + new emulsifier 20 gal 4.3 90.7Spray Oil 15 + known emulsifier 20 gal 4.9 68.0 Spray Oil 22 + newemulsifier 10 gal 2.1 85.3 Spray Oil 22 + known emulsifier 10 gal 8.786.7 Spray Oil 22 + new emulsifier 20 gal 5.3 83.3 Spray Oil 22 + knownemulsifier 20 gal 3.8 90.7 Sunspray 435 oil 10 gal 5.3 86.0

When Spray Oils 13, 15 and 22 are compared at 10 and 20 gallonapplication rates across all of the different formulations, the 20-galrate increased the percentage of marketable fruit compared to the 10-galrate. In addition, the addition of the emulsifier of the presentinvention to Spray Oils 13 and 15 markedly increased the percentage ofmarketable fruit as compared to the use of the known emulsifier whencombined with these same spray oils.

EXAMPLE VIII

Spray oils were evaluated for phytotoxicity to fruit and leaves incitrus—with the tests conducted on California oranges. Treatments inquarts/acre of various oil/emulsifier compositions were tested in arange of water concentrations. Phytotoxicity of leaves and fruit weremeasured at various intervals, with phytotoxicity of leaves and fruitsummarized below in Table VIII, as measured on Sep. 2, 1999(mid-season), with phytotoxicity of fruit also measured just prior toharvest (Dec. 29, 1999).

TABLE VIII Applicat'n Water Sept. 2, 1999 Sept. 2, 1999 Dec. 29, 1999rate per phytoxicity phytoxicity phytoxicity Treatment Description peracre acre leaves fruit fruit Control None none 0.0 0.0 0.0 Spray Oil 10new emulsifier  72 qt 1500 gal 1.3 2.0 0.7 Spray Oil 13 new emulsifier 72 qt 1500 gal 2.0 2.0 0.0 Spray Oil 22 new emuisifier  72 qt 1500 gal3.0 3.0 0.0 Spray Oil 10 new emulsifier  72 qt  750 gal 1.3 2.0 0.0Spray Oil 13 new emulsifier  72 qt  750 gal 2.0 2.0 0.0 Spray Oil 22 newemulsifier  72 qt  750 gal 2.7 2.7 0.0 Spray Oil 10 new emulsifier  72qt  250 gal 2.0 2.0 0.0 Spray Oil 13 new emulsifier  72 qt  250 gal 3.01.7 0.0 Spray Oil 22 new emulsifier  72 qt  250 gal 3.0 3.0 0.0 Exxon796 conven emulsifier  72 qt 1500 gal 3.0 3.0 0.0 Exxon 796 convenemulsifier  72 qt  750 gal 2.3 2.0 0.0 Exxon 796 conven emulsifier  72qt  250 gal 4.0 3.0 2.0 Spray Oil 13 new emulsifier 144 qt 1500 gal 3.73.0 4.0 Spray Oil 13 new emulsifier 144 qt  250 gal 4.0 4.7 3.7 Exxon796 conven emulsifier 144 qt 1500 gal 4.0 5.0 4.0 Exxon 796 convenemulsifier 144 qt  250 gal 4.3 6.0 4.0

Referring now to Table VIII, it can be seen that application ofhydroisomerized oils with the emulsions of the present inventiongenerally resulted in lowered mid-season leaf phytotoxicity than sprayoils mixed with a conventional emulsifier. Moreover, at the 72 quart peracre application rate, the hydroisomerized oils in combination with anemulsion of the present invention had no appreciable fruit phytotoxicityjust prior to harvest, with the 144 quart per acre application rateexhibiting fruit phytotoxicity at rates similar to that of the Exxon 796product.

EXAMPLE IX

Spray oils were evaluated for effectiveness in achieving early controlof citrus rust mite populations in grapefruit groves in Lake Alfred,Fla. In each case, control plots were maintained to track when thenatural growth and subsidence of the rust mite population, it beingunderstood that if the natural growth of the rust mite population isallowed to occur, damage to marketable fruit quality and/or yield willprobably have occurred, making it important to accelerate the decline ofthe rust mite population in advance of the natural subsidence. SprayOils 10, 13, 15 and 22 emulsified with an emulsifier composition of thepresent invention, which was applied to 10 year old trees at 10 or 15gallons/acre rates with a Durant Wayland PTO-driven speed sprayercalibrated for 125 gallons/acre. The treated trees were compared withuntreated control trees and with trees sprayed with a standard spray oilemulsified with T-Mulz. Rust mite infestion was rated prior toapplication and at identified intervals post application. Results aresummarized below in Table IX.

TABLE X 3 days 6 days 12 days 25 days Applica- prior to post post posttion treat- treat- treat- treat- Treatment Description rate/acre mentment ment ment Control None 19.38 46.49 48.97 9.66 Spray Oil 22 10 gal35.82 0.05 0.02 0.06 Spray Oil 22 15 gal 13.41 0.55 0.13 0.03 Spray Oil15 10 gal 19.51 0.52 0.08 0.00 Spray Oil 15 15 gal 19.26 1.11 0.15 0.15Spray Oil 13 10 gal 39.28 1.28 0.63 0.13 Spray Oil 13 15 gal 9.55 0.250.31 0.03 Spray Oil 10 10 gal 6.66 0.53 0.20 0.08 Spray Oil 10 15 gal19.41 0.44 0.04 0.03 Conventional spray oil 10 gal 16.27 2.12 0.65 0.27Conventional spray oil 15 gal 17.93 0.03 0.01 0.01

EXAMPLE X

In the tests below, Spray Oils 13, 15 and 22 emulsified with theemulsifier composition of the present invention, were tested atdiffering application rates and compared with an untreated control and astandard spray oil emulsified with T-Mulz. A first treatment was madepostbloom (in late April) followed by a second treatment in mid-summer(mid-July). Rust mite infestion was rated at mites/cm² prior to the2^(nd) application, and at identified intervals post 2^(nd)-application.Results are summarized below in Table X.

TABLE IX 19 days 7 days 23 days 31 days prior to post post post Applica-2^(nd) 2^(nd) 2^(nd) 2^(nd) tion treat- treat- treat- treat- TreatmentDescription rate/acre ment ment ment ment Control None 27.4 30.2 6.3 1.2Spray Oil 13 10 gal 0.82 0.07 0.12 0.45 Spray Oil 13 20 gal 0.16 0.090.08 0.07 Spray Oil 15 10 gal 0.23 0.11 0.39 0.30 Spray Oil 15 20 gal0.37 0.02 0.07 0.07 Spray Oil 22 10 gal 0.14 0.04 0.12 0.02 Spray Oil 2220 gal 0.11 0.00 0.00 0.01 Conventional spray oil 10 gal 0.15 0.31 0.150.17 Conventional spray oil 20 gal 0.77 0.00 0.01 0.03

EXAMPLE XI

In the tests below, Spray Oils 13, 15 and 22 were mixed to form acomposition including (a) 1.2% by weight of emulsifier composition ofthe present invention, (b) 1.6% by weight of the emulsified compositionof the present invention, or (c) 1% by weight of TMulz-A02 (Spray Oil 22only), and applied with a hand gun at either 10 or 20 gallons per acre,and compared with an untreated control and a standard spray oilemulsified with T-Mulz-A-02. A first treatment was made postbloom (inlate April) followed by a second treatment in mid-summer (mid-July) anda third treatment at the end of September. Rust mite infestion was ratedat mites/cm² throughout the season. However, of particular interest arethe infestation measurements made just prior to and after the 3^(rd)application, when the rust mite infestation was naturally peaking, asevidenced by the control measurements. Results are summarized below inTable XI.

TABLE XI 10 days 6 days 14 days 2 days prior to post post post Applica-3^(rd) 3^(rd) 3^(rd) 3^(rd) tion treat- treat- treat- treat- TreatmentDescription rate/acre ment ment ment ment Control None 32.5 7.00 4.7 1.9Spray Oil 13 (a) 10 gal 15.40 1.10 0.75 0.95 Spray Oil 13 (a) 10 gal4.10 2.00 1.40 0.21 Spray Oil 13 (b) 20 gal 8.80 1.80 0.27 0.49 SprayOil 13 (b) 20 gal 12.30 1.30 0.14 0.32 Spray Oil 15 (a) 10 gal 3.30 0.730.11 0.03 Spray Oil 15 (a) 10 gal 4.30 0.28 0.01 0.08 Spray Oil 15 (b)20 gal 10.50 0.42 0.02 0.27 Spray Oil 15 (b) 20 gal 4.90 0.66 0.17 0.23Spray Oil 22 (a) 10 gal 3.40 0.19 0.07 0.05 Spray Oil 22 (a) 10 gal 0.230.07 0.03 0.00 Spray Oil 22 (b) 20 gal 2.50 0.53 0.41 0.34 Spray Oil 22(b) 20 gal 0.25 0.01 0.24 0.21 Spray Oil 22 (c) 10 gal 7.70 0.77 0.790.21 Spray Oil 22 (c) 20 gal 18.90 0.82 0.39 0.39 Conventional spray oil10 gal 9.90 0.14 0.11 0.07 Conventionai spray oil 20 gal 8.30 0.13 0.000.09

It can be seen that hydroisomerized spray oils, when mixed with anemulsifier composition of the present invention, were effective inaccelerating the decline in citrus rust mite population.

Having described the techniques of the present invention, it can now beappreciated that the emulsion blends of the present invention containingethoxylated alcohols containing primarily hydrocarbons of C10-C16,preferably having on average at least 2.8 ethoxy and/or alcohol groupsper chain, together with a glycerol mono- and/or dioleate, in a mostpreferred ratio of from 9:1 to 4:6. As will be appreciated by those ofordinary skill in the art, while a combination of glycerol mono- and/ordioleates are preferred, glycerol mono-, di- and trioliates may be usedalone or in mixtures of varying proportions, The emulsion blends of thepresent invention are particularly useful when mixed with hydrocrackingand/or hydroisomerized oils and water, which may be subsequentlyemployed as a spray oil for agricultural purposes. The emulsion blendsof the present invention also find particular utility when mixed withconventional spray oils and hard water.

Reference has been made in detail to presently preferred embodiments ofthe invention. It is intended that all matter contained in thedescription above shall be interpreted as illustrative and not in alimiting sense. Moreover, other embodiments of the invention will beapparent to those skilled in the art from consideration of thespecification and practice of the invention disclosed herein. It isintended that the specification and examples be considered as exemplaryonly, with the true scope and spirit of the invention being indicated bythe following claims.

What is claimed is:
 1. A technique for minimizing pest infestations inagricultural acreage comprising: combining a spray oil with anemulsifier blend, said emulsifier blend comprising: ethoxylated alcoholscontaining primarily C10-C16 carbon chains with an average of 2.8 ormore ethoxy and/or alcohol groups per carbon chain, and glycerol mono-and/or dioleates, wherein the emulsifier blend contains from 90% to 40%by weight of ethoxylated alcohols and from 10% to 60% by weight of theglycerol mono- and/or dioleates; emulsifying spray oil with theemulsifier blend in water; and spraying the spray oil and emulsifierblend emulsion on the agricultural acreage.
 2. The technique forminimizing pest infestations in agricultural acreage of claim 1, whereinthe spray oil is a hydrocracked and/or hydroisomerized oil.
 3. Thetechnique for minimizing pest infestations in agricultural acreage ofclaim 1, wherein the hydrocracked and hydroisomerized oil has a saturatecontent of ≧99%.
 4. The technique for minimizing pest infestations inagricultural acreage of claim 1, wherein the emulsifier blend contains aratio by weight of ethoxylated alcohols:glycerol mono- and/or dioleatesof approximately 4:1.
 5. The technique for minimizing pest infestationsin agricultural acreage of claim 1 wherein the spray oil and emulsifierblend are combined in a ratio of from about 99:1 to 98:2.